EP2499183B1 - Polyesters pour revêtements - Google Patents

Polyesters pour revêtements Download PDF

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Publication number
EP2499183B1
EP2499183B1 EP20100775838 EP10775838A EP2499183B1 EP 2499183 B1 EP2499183 B1 EP 2499183B1 EP 20100775838 EP20100775838 EP 20100775838 EP 10775838 A EP10775838 A EP 10775838A EP 2499183 B1 EP2499183 B1 EP 2499183B1
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Prior art keywords
polyester
functional
hydroxyl
weight
meth
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German (de)
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EP2499183A1 (fr
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Luc Moens
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Allnex Belgium NV SA
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Allnex Belgium NV SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to polyesters that can be prepared from renewable resources and/or recycled materials, to their use and their production process.
  • Carboxyl-, hydroxyl- and (meth)acryloyl-functional polyesters and their use in resins and/or binders for coatings have been widely described.
  • Non-renewable resources are taken from the earth, and once taken they are not replaced.
  • a sustainable path forward in replacing some non-renewable resources is recycling, meaning that starting materials are recovered from their prior use to be used again.
  • PET polyethylene terephthalate
  • DD 295,647 relates to the synthesis of carboxyl functional polyesters for powder coatings obtained from reacting high number average molecular weight PET waste polyacids and polyols.
  • thermosetting polyterephthalate binders prepared from mixing a hydroxyl functional polyterephthalate and a carboxyl functional polyterephthalate. Both polyterephthalates are obtained from glycolysis of PET with alcohols.
  • Non-renewable resources may also be replaced (partially or completely) by renewable resources.
  • renewable resources The interest of the industry for renewable resources is driven by an awareness of the environmental consequences of depletion of feedstock based on fossil fuels.
  • WO 2008/031592 discloses a process for the production of a polyester from a mixture of isoidide, and a dicarboxylic acid or dicarboxylic acid anhydride. Only coatings obtained from polyesters made from succinic acid as sole polyacid and from isosorbide as sole polyol have a flexibility and glass transition temperature acceptable for powder coatings.
  • polyesters that can be prepared from recycled materials and/or renewable resources in an easy way and that can be used in various types of coatings.
  • polyesters comprising moieties of terephthalic acid and/or isophthalic acid, of ethylene glycol, of a dianhydrohexitol (e.g. isosorbide), and, advantageously, of one or more linear chain dicarboxylic acids.
  • Moieties as used herein is meant monomer units.
  • polyesters of the invention are non-thermoplastic. Preferred are thermosetting polyesters, but radiation curable polyesters are also possible.
  • Polyesters of the invention can be used as part of the binder system of coatings, of which powder coatings are just one example.
  • the polyesters according the present invention can, however, also be used in a liquid coating composition.
  • the liquid coating composition according to the invention may be water-borne or solvent-borne.
  • a process to produce a polyester comprising a step of (1) glycolysis of a polyethylene terephthalate and/or a polyethylene isophthalate with a dianhydrohexitol, followed, where needed, by (2) one or more additional steps, more in particular one or more additional reaction steps.
  • one or more other polyols e.g. glycerol and/or sorbitol
  • dianhydrohexitol e.g. isosorbide
  • polyesters can be produced that are hydroxyl-functional or carboxyl-functional, and that have a number average molecular weight (Mn), as measured by gel permeation chromatography (GPC), of from 300 to 15000 daltons.
  • Mn number average molecular weight
  • GPC gel permeation chromatography
  • the Mn of the polyesters is at least 350 daltons, preferably at least 400 daltons, more in particular at least 550 daltons.
  • the Mn typically varies according to the type and nature of coating wherein the polyester is used, and typically is measured via GPC using polystyrene standards.
  • glycolysis with a dianhydrohexitol, and optionally one or more other polyols is performed at a temperature and for a time sufficient to obtain transesterification.
  • other polyols e.g. glycerol and/or sorbitol
  • step (1) advantageously is performed under temperature conditions of from 200 °C to 260 °C.
  • the temperature throughout step (1) is below 250 °C. More preferably step (1) is performed under temperature conditions of from 220 °C to 240 °C.
  • Step (1) in the process of the invention preferably proceeds in the presence of a transesterification catalyst.
  • transesterification catalysts include n-butyltin trioctoate and/or tetra-n-butyltitanate.
  • hydroxyl-functional polymers of the desired molecular weight can be obtained after step (1) of the process of the invention.
  • step (1) will be followed by one or more additional steps, more in particular one or more additional reaction steps.
  • additional steps advantageously lead to polyesters with the desired properties, such as the desired molecular weight, the desired degree of condensation etc.
  • the additional steps may comprise steps of vacuum, chain extension, carboxylation and/or other suitable steps.
  • step (1) in the process is followed by a step (2) comprising a step of chain extension and/or carboxylation.
  • chain extension may be obtained by applying a reduced pressure ( ⁇ 1 atm) or vacuum (e.g. 50 mm Hg) and/or by reacting a hydroxyl-functional prepolymer previously obtained (in step 1) with one or more polyacids, preferably one or more linear chain dicarboxylic acids and, optionally, one or more other polyacids.
  • a reduced pressure ⁇ 1 atm
  • vacuum e.g. 50 mm Hg
  • a reduced pressure or vacuum may be used to distill of ethylene glycol until the desired hydroxyl number is obtained.
  • a reduced pressure or vacuum may be applied to distill of part of the ethylene glycol, followed by a condensation reaction with one or more polyacids, preferably one or more linear chain dicarboxylic acids and, optionally, one or more other polyacids.
  • the final weight ratio of dianhydrohexitol to linear dicarboxylic acid is from 0.3 to 2.5, typically from 0.5 to 2, and preferably from 0.7 to 1.4.
  • Tg values as known may vary and be adapted to the end use.
  • carboxylation e.g. is obtained by reacting a hydroxyl-functional prepolymer previously obtained (in step 1, possibly followed by a step of reduced pressure or vacuum) with one or more polyacids.
  • polyacids Preferred are linear chain dicarboxylic acids, which may be used alone or in combination with one or more other polyacids.
  • one or more polyacids are used for said chain extension and/or said carboxylation.
  • Preferred polyacids for use in said chain extension and/or said carboxylation step are linear chain dicarboxylic acids.
  • Said linear chain dicarboxylic acids may be used alone or in combination with one or more other polyacids.
  • other is meant in this context different from the linear chain dicarboxylic acid(s) used (e.g. succinic acid).
  • At least one, and more preferably all, of the polyacids used for said chain extension and/or said carboxylation in step (2) are renewable polyacids.
  • the step of chain extension and/or carboxylation in the process of the invention is followed by a step of reduced pressure ( ⁇ 1 atm) or vacuum (e.g. 50 mm Hg).
  • a reduced pressure or vacuum is applied until the desired degree of condensation is obtained.
  • step (2) and more in particular the step of chain extension and/or carboxylation therein, is performed under temperature conditions of from 120 °C to 260 °C, in particular from 200 °C to 260 °C. More preferably step (2), and more in particular the step of chain extension and/or carboxylation therein, is performed at temperatures below 250 °C, more in particular at temperatures between 220 °C and 240 °C.
  • reaction temperature in step 2 typically is between 120 °C and 240 °C, preferably between 160 °C and 200 °C.
  • the polyethylene terephthalate and/or polyethylene isophthalate used as starting material in the process of the invention may be provided under the form of a material (or reactant) comprising said polyethylene terephthalate and/or said polyethylene isophthaltate.
  • the material advantageously is a recycled material.
  • the material comprising recycled polyethylene terephthalate is recycled polyethylene terephthalate, more in particular PET scrap.
  • non-recycled PET or virgin PET
  • virgin PET can also be used instead of the recycled PET.
  • a polyethylene isophthalate as reactant in step (1) of the process of the invention is particularly advantageous to improve outdoor durability.
  • a polyethylene isophthalate first is prepared through the direct condensation of ethylene glycol and isophthalic acid and/or dimethylisophthalate. Such a polyethylene isophthalate is then subjected to a step of glycolysis as described in step (1) of the process of the invention.
  • the polyethylene isophthalate can be prepared in the same or in another reactor. Alternatively recycled polyethylene isophthalate can be used.
  • the polyethylene terephthalate and/or the polyethylene isophthalate is the sole source of ethylene glycol and of terephthalic acid and/or isophthalic acid incorporated into the polyesters of the invention.
  • the present invention also relates to polyesters obtainable by (or obtained by) the process of the invention.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention may further, optionally, comprise moieties (e) of one or more other polyols (e1) and/or of one or more other polyacids (e2).
  • polyols (e1) is meant a polyol different from said dianhydrohexitol.
  • the polyol is also different from ethylene glycol.
  • the other polyol (e1) is different from moieties (b) and (c).
  • polyacids (e2) is meant a polyacid different from the linear chain dicarboxylic acids (d).
  • the polyacid is also different from terephthalic acid and/or isophthalic acid.
  • the other polyacid (e2) is different from moieties (a) and (d).
  • the other polyacid (e2) is not a fatty acid, in particular is not a saturated or an unsaturated dimer or trimer fatty acid.
  • linear chain dicarboxylic acid (d) is not a fatty acid, in particular is not a saturated or an unsaturated dimer fatty acid.
  • the linear chain dicarboxylic acids (d) and the other polyacids (e2) that are used in the preparation of hydroxyl-functional polyesters, and in particular in the preparation of carboxyl-functional polyesters of the invention are different from a fatty acid, more in particular are different from a saturated or an unsaturated dimer or trimer fatty acid.
  • hydroxyl-functional or carboxyl-functional polyesters of the invention comprise, based on the total weight of the polyester, less than 20% by weight, typically less than 5% by weight, preferably less than 1% by weight, more preferably less than 0.1 % by weight of fatty acid moieties.
  • hydroxyl-functional or carboxyl-functional polyesters of the invention and in particular carboxyl-functional polyesters of the invention, comprise no fatty acid moieties, in particular comprise no saturated or unsaturated dimer or trimer fatty acid moieties, more in particular comprise no saturated dimer fatty acid moieties.
  • the weight percentages of the moieties (a), (b), (c), (d) and of the optional moieties (e1) and/or (e2) sum up to 100%.
  • Hydroxyl-functional or carboxyl-functional polyesters of the invention advantageously have a number average molecular weight, as measured by gel permeation chromatography (GPC), of from 300 to 15000 daltons, preferably from 350 to 15000 daltons, in particular from 500 to 15000 daltons.
  • the Mn of the polyesters is at least 400 daltons.
  • the Mn is at least 550 daltons, more preferably at least 750 daltons, most preferably at least 1100 daltons.
  • the Mn is at most 11000 daltons, more preferably at most 8500 daltons, depending on the type of coating wherein the polyester is used.
  • the Mn is measured by GPC using polystyrene standards.
  • Mn is measured by GPC in THF (tetrahydrofuran) on a 3xPLgel 5 ⁇ m Mixed-D LS 300x7.5mm column MW range 162 to 377400 g/mol calibrated with polystyrene standards, at 40 °C. Typically Refractive Index (RI) is used as detector.
  • RI Refractive Index
  • Hydroxyl-functional or carboxyl-functional polyesters of the invention preferably are prepared from, based on the total weight of the polyester, 5% to 35% by weight of moieties of ethylene glycol (b).
  • the amount of ethylene glycol moieties in the polyester preferably is at least 10% by weight, typically at least 12% by weight, often at least 15% by weight. Typically the amount of ethylene glycol moieties in the polyester does not exceed 30% by weight.
  • Preferred hydroxyl-functional or carboxyl-functional polyesters of the invention comprise, based on the total weight of the polyester:
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention comprise at least 30 % by weight and preferably at most 60 % by weight of terephthalic acid moieties and/or of isophthalic acid moieties.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention comprise at least 10 % by weight, typically at least 12% by weight, often at least 15% by weight, and preferably at most 30 % by weight of ethyelene glycol moieties.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention comprise at least 10 % by weight and preferably at most 30 % by weight of dianhydrohexitol moieties.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention comprise at least 10 % by weight of linear dicarboxylic acid moieties and preferably at most 30 % by weight of linear dicarboxylic acid moieties.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention optionally, comprise from 0 to 35% by weight, generally from 0 to 20 % by weight of one or more other polyol moieties and/or one or more other polyacid moieties.
  • Weight percentages are herein on the total weight of the polyester. In an embodiment according to the present invention, the weight percentages of the moieties (a) through (e) as identified above sum up to 100%.
  • the hydroxyl-functional or carboxyl-functional polyesters of the invention are derived from materials based on a polyethylene terephthalate and/or a polyethylene isophthalate that is glycolysed in the presence of a dianhydrohexitol and further reacted with one or more linear chain dicarboxylic acids.
  • terephthalic acid and/or isophthalic acid moieties (a) present in the polyesters of the invention are derived from a di-alkyl terephthalate and/or dialkylisophthalate. Preferably this percentage is below 5% by weight.
  • Weight percentages are herein on the total weight of the polyester.
  • dianhydrohexitol used in the synthesis of the hydroxyl-functional or carboxyl-functional polyesters of the present invention, refers to any of the three isomers of a dianhydrohexitol , i.e. isosorbide, isoide and/or isomannide.
  • the three isomers may be used alone or as a mixture of two or three of the isomers.
  • the dianhydrohexitol (c) comprises at least isosorbide, optionally in combination with at least one of isoide and isomannide. Most preferably the dianhydrohexitol (c) is isosorbide.
  • the dianhydrohextiol, preferably isosorbide, may be a renewable polyol.
  • the linear chain dicarboxylic acids (d), used in the synthesis of the hydroxyl-functional or carboxyl-functional polyesters of the present invention preferably are linear chain aliphatic dicarboxylic acids that advantageously are selected from succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and possibly from dimer diacids such as Empol® 1018 or Pripol® 1013.
  • succinic acid in particular succinic acid obtained from renewable resources.
  • adipic acid in particular adipic acid obtained from renewable resources.
  • dimer diacids in particular dimer diacids obtained from renewable resources.
  • the linear chain dicarboxylic acid (d) that is used in the synthesis of the polyesters of the invention, more in particular in the synthesis of the carboxyl-functional polyesters of the present invention is not a fatty acid, or is not derived from a fatty acid, more in particular is not a saturated or an unsaturated dimer fatty acid.
  • the other polyols (e1) used in the synthesis of the hydroxyl-functional or carboxyl-functional polyesters of the present invention, are preferably selected from neopentyl glycol, diethylene glycol, propyleneglycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 2-ethyl, 2-butyl-1,3-propanediol, 1-ethyl-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, hydrogenated Bisphenol A, hydroxypivalate of neopentyl glycol, glycerol, sorbitol, trimethylolpropane, ditrimethyl
  • the other polyacids (e2) used in the synthesis of the hydroxyl-functional or carboxyl-functional polyesters of the present invention, are preferably selected from fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, citric acid, tartaric acid, trimellitic acid, pyromellitic acid, or the corresponding anhydrides (of any of these).
  • Preferred hydroxyl-functional or carboxyl-functional polyesters of the invention have an acid number or a hydroxyl number of from 10 to 310 mg KOH/g.
  • the acid number or the hydroxyl number is at least 15 mg KOH/g, more preferably at least 20 mg KOH/g.
  • the acid number or the hydroxyl number is at most 200 mg KOH/g, often at most 150 mg KOH/g, more preferably at most 100 mg KOH/g, though this may depend on the nature of the coating wherein they are used.
  • Preferred hydroxyl-functional or carboxyl-functional polyesters of the invention are characterized by a glass transition temperature (Tg), measured by Differential Scanning Calorimetry according to ASTM D3418 with a heating gradient of 20°C per minute, of less than 120 °C, more preferably less than 100 °C and most preferably less than 80 °C.
  • Tg glass transition temperature
  • the Tg is at least 40 °C, more preferably at least 45 °C, most preferably at least 50 °C if the polyester is to be used in a powder coating.
  • polyesters are used with a Tg of at least -100°C, preferably at least -50°C, more preferably at least -20°C.
  • Preferred hydroxyl-functional or carboxyl-functional polyesters of the invention have a Brookfield (cone/plate) viscosity accordingly to ASTM D4287-88, of from 50 mPa.s at room temperature (e.g. 25°C) to 15000 mPa.s at 200 °C.
  • the Brookfield (cone/plate) viscosity at room temperature e.g. 25 °C
  • the Brookfield (cone/plate) viscosity at room temperature is at least 500 mPa.s, more preferably at least 700 mPa.s.
  • the Brookfield (cone/plate) viscosity at 200 °C is at most 12000 mPa.s, more preferably at most 10000 mPa.s.
  • hydroxyl-functional and/or carboxyl-functional polyesters of the invention are amorphous polyesters.
  • Hydroxyl-functional or carboxyl-functional polyesters of the invention are preferably obtained from the transesterification (also referred to as glycolysis) of recycled polyethylene terephthalate with dianhydrohexitol, preferably isosorbide, and, optionally, one or more other polyols, such as glycerol and/or sorbitol.
  • Another example of such other polyol is 1,3-propanediol.
  • a linear chain dicarboxylic acid preferably succinic acid, and, optionally, one or more other polyacids is added.
  • the polycondensation is continued, first under atmospheric pressure, then under reduced pressure until the right polyester characteristics are obtained.
  • the dianhydrohexitol together with another polyol preferably glycerol
  • a conventional reactor equipped with a stirrer, an inert gas (e.g. nitrogen) inlet, a thermocouple, a distillation column connected to a water-cooled condenser, a water separator and a vacuum connection tube and heated to 160 °C.
  • a transesterification catalyst such as n-butyltin trioctoate or tetra-n-butyltitanate is present as well.
  • the (recycled) polyethylene terephthalate is gradually added under stirring meanwhile the temperature is increased to 230 °C.
  • stirring is continued, under nitrogen atmosphere, for another 3 hours.
  • a vacuum step here can be applied until the assumed hydroxyl number is obtained.
  • the reactor content is cooled down to a temperature of from 160 °C to 200 °C and the linear chain diacarboxylic acid, preferably succinic acid is added, optionally along with one or more other polyacids.
  • a condensation catalyst, such as n-butyltin trioctoate may be added.
  • the reactor content is heated again to 230 °C.
  • the reactor content then is stirred for another two hours at 230 °C under N 2 (nitrogen) atmosphere at atmospheric pressure. Vacuum then is applied and the degree of esterification followed by determining the amount of water formed in the course of the reaction and the properties of the obtained polyester, for example the hydroxyl number, the acid number, the molecular weight or the viscosity.
  • colour stabilisers for example, phenolic antioxidants such as IRGANOX® 1010 (Ciba) or phosphonite- and phosphite-type stabilisers such as tributylphosphite, can be added in an amount from 0 to 1 % by weight of the reactants.
  • phenolic antioxidants such as IRGANOX® 1010 (Ciba)
  • phosphonite- and phosphite-type stabilisers such as tributylphosphite
  • tributylphosphite phosphonite- and phosphite-type stabilisers
  • 2-phenylimidazoline 2-phenylimidazoline
  • phosphines e.g. triphenylphosphine
  • ammonium salts e.g. tetrabutylammonium bromide or tetrapropylammonium chloride
  • phosphonium salts e.g. ethyltriphenylphosphonium bromide, tetrapropylphosphonium chloride
  • tin catalysts e.g. dibutyltin dilaurate
  • bismuth catalysts e.g. bismuth neodecanoate
  • zinc catalysts e.g. zinc octoate
  • the dianhydrohexitol, the linear chain dicarboxylic acid, the other polyacids and/or the other polyols used in the preparation process of the invention can be obtained from renewable resources.
  • the polyesters of the invention are prepared from reactants comprising (or including) recycled polyethylene terephthalate and/or recycled polyethylene isophthalate, and from one or more polyols and/or polyacids, wherein at least one of the polyols and/or polyacids is obtained from renewable resources.
  • reactants comprising (or including) recycled polyethylene terephthalate and/or recycled polyethylene isophthalate, and from one or more polyols and/or polyacids, wherein at least one of the polyols and/or polyacids is obtained from renewable resources.
  • Preferably all polyols and/or polyacids used are obtained from renewable resources.
  • the polyesters of the invention are prepared from reactants comprising (or including) recycled polyethylene terephthalate and from one or more polyols and/or polyacids, wherein at least one of the polyols and/or polyacids is obtained from renewable resources.
  • the polyesters of the invention are prepared from reactants comprising (or including) recycled polyethylene terephthalate and from one or more polyols and/or polyacids, wherein at least one of the polyols and/or polyacids is obtained from renewable resources.
  • Preferably all polyols and/or polyacids used are obtained from renewable resources.
  • the polyols and/or polyacids obtained from renewable resources are preferably obtained from bio-based feedstocks such as vegetable oils, starch, cellulose/pulp, sugar, natural fibers and/or other vegetable raw materials.
  • thermosetting coating composition can be used in a thermosetting coating composition and/or in a radiation curable coating composition.
  • the thermosetting coating composition may be a powder coating composition or a liquid coating composition.
  • the liquid coating composition according to the invention may be water-borne or solvent-borne. An aspect of the invention concerns such coating compositions.
  • thermosetting coating compositions of the invention comprise at least one hydroxyl-functional and/or at least one carboxyl-functional polyester of the invention, along with a crosslinker having functional groups reactable with the polyesters' functional groups.
  • a crosslinker having functional groups reactable with the polyesters' functional groups may be desired.
  • thermosetting coating compositions of the invention Upon application and curing at temperatures between room temperature (e.g. 25°C) and 200 °C, the thermosetting coating compositions of the invention advantageously result in coatings exhibiting excellent flow and outstanding flexibility. For powder coatings curing temperatures are often between 100 °C and 200 °C.
  • polyester polyols are used.
  • the polyester solutions used are preferably characterized by a mass fraction of solids of at least 60 %, advantageously of at least 70 %, more preferably of at least 75 % (determined according to DIN EN ISO 3251). Preferable the mass fraction of solids does not exceed 99 %.
  • the polyester solutions are preferably characterized by a dynamic viscosity (according to DIN EN ISO 3219 at 23 °C) of from 50 to 35000 mPa.s.
  • the viscosity is at least 500 mPa.s, more preferably at least 1000 mPa.s, most preferably at least 1500 mPa.s.
  • the viscosity is at most 30000 mPa.s, more preferably at most 25000 mPa.s, most preferably at most 20000 mPa.s.
  • the polyesters used therein have a hydroxyl (OH) number on the solid resin (according to DIN EN ISO 4629) of between 10 and 310 mg KOH/g, more preferably of between 10 and 300 mg KOH/g.
  • OH number is at least 50 mg KOH/g, more preferably at least 80 mg KOH/g, most preferably at least 100 mg KOH/g.
  • the OH number is at most 250 mg KOH/g.
  • Polyester polyols used in liquid coating compositions typically are low molar mass polyester polyols.
  • the low molar mass polyester polyols used may be chemically or physically modified by reaction, for example, with isocyanate compounds or compounds which comprise oxirane groups. Other possible modifications include the incorporation of low molar mass urea derivatives.
  • the polyester polyols may also be the basis of (grafted-on) acrylate polymers, such as described in US 6,258,897 , EP 0776920 and EP 0896991 , the content of which is incorporated herein by reference.
  • the polyester according to the present invention partially can be replaced by an acrylic resin.
  • the liquid coating composition thus comprises at least one acrylic resin and at least one polyester resin in a ratio of polyester resin:acrylic resin of between 4:1 and 2:1, preferably between 3.5:1 and 2.5:1, more preferably between 3.2:1 and 2.2:1, most preferably between 3:1 and 2.2:1.
  • the liquid coating composition used in the process according to the invention further comprises at least one hardener.
  • Suitable hardeners are well known in the art.
  • Possible hardeners include (blocked or non-blocked) polyisocyanates, amino resins, phenolic resins, polycarboxylic acids and their anhydrides (see e.g. US 6,258,897 ).
  • Polyisocyanates in non-blocked form may be used for curing at moderate temperatures or at room temperature.
  • blocked polyisocyanates and also polycarboxylic acids and their anhydrides are additionally suitable.
  • Amino resins are preferred hardeners (or curing agents), more in particular urea resins, melamine resins and/or benzoguanamine resins. These are etherified urea-, melamine- or benzo-guanamine-formaldehyde condensation products, respectively. Particularly preferred are melamine resins and especially high solids methylated melamine resins such as hexamethoxymethylmelamine resins.
  • High solids in this context refers to a mass fraction of solids of at least 70 %, in particular at least 75 %, preferably at least 95 %.
  • Suitable hardeners are e.g. hexamethoxymethylmelamine resins with a mass fraction of solids above 98 %.
  • Other preferred examples include high imino resins with a mass fraction of solids in the range of 78 % to 82 %.
  • an acid catalyst is added when amino resins are used as hardener.
  • the liquid coating composition used further comprises an acid catalyst.
  • Fully alkylated amino resins often require a strong acid catalyst such as CYCAT® 4045, whereas partially alkylated and high imino resins in general only need a weak acid catalyst. Also urea and glycoluril resins respond better to a strong acid catalyst.
  • catalysts examples include amine blocked p-toluene sulfonic acid (pTSA), dimethyl pyrophosphate (DMAPP), dodecylbenzenesulfonic acid (DDBSA) and dinonylnaphthalenedisulfonic acid (DNNDSA).
  • pTSA amine blocked p-toluene sulfonic acid
  • DMAPP dimethyl pyrophosphate
  • DBSA dodecylbenzenesulfonic acid
  • DNNDSA dinonylnaphthalenedisulfonic acid
  • Preferred catalysts are amine blocked p-toluene sulfonic acids like ADDITOL® VXK 6395 and CYCAT® 4045.
  • the mass fraction of the resin(s) in the liquid coating composition is between 10 % and 90 %.
  • the mass fraction of the resins is at least 20 %, more preferably at least 50 %.
  • the mass fraction of the resins is at most 85 %, more preferably at most 80 %.
  • the mass fraction of the hardener in the liquid coating composition is between 5 % and 70 %.
  • the mass fraction of the hardener is at least 10 %, more preferably at least 12 %.
  • the mass fraction of the hardener is at most 40 %, more preferably at most 25 %.
  • the ratio of the mass fractions of the resin(s) and the hardener(s) preferably is between 6:1 and 1:1, more in particular between 5:1 and 2:1.
  • the mass fraction of the optional acid catalyst in the liquid coating composition is between 0 % and 10 %, more in particular between 0.1 % and 10 %.
  • the mass fraction of the optional catalyst is at least 0.3 %.
  • the mass fraction of the optional catalyst does not exceed 8 %.
  • suitable solvents for the resins and in particular the preferred oligoester polyols and/or acrylic resins of the invention include aliphatic, cycloaliphatic and aromatic hydrocarbons, such as alkylbenzenes, e.g., xylene, toluene; esters, such as ethyl acetate, butyl acetate, acetates with longer alcohol residues, butyl propionate, pentyl propionate, ethylene glycol monoethyl ether acetate, the corresponding methyl ether acetate, and propylene glycol methyl ether acetate; ethers, such as ethylene glycol monoethyl, monomethyl or monobutyl ether; glycols; alcohols; ketones such as methyl isoamyl ketone and methyl isobutyl ketone; lactones, and mixtures of such solvents.
  • alkylbenzenes e.g., xylene, tol
  • solvents which can be used include reaction products of lactones with glycols or alcohols. Particularly preferred are mixtures of a dimethylester (like DME-1, a santosol dimethylester of adipic, glutaric & succinic acid) and S-100 (an aromatic hydrocarbon solvent from HuaLun Chemistries). Butanol may help stabilize paint storage.
  • a dimethylester like DME-1, a santosol dimethylester of adipic, glutaric & succinic acid
  • S-100 an aromatic hydrocarbon solvent from HuaLun Chemistries
  • the mass fraction of the optional solvents in the liquid coating composition typically is between 0 % and 50 %.
  • the mass fraction of the optional solvents is at least 5 %, more preferably at least 10 %.
  • the mass fraction of the optional solvents is at most 40 %, more preferably at most 30 %.
  • the liquid coating composition of the invention may further comprise pigments and/or colorants and/or fillers.
  • fillers include talc, mica, kaolin, chalk, quartz flour, slate flour, various silicas, silicates, etc.
  • the mass fraction of the optional pigments and/or colorants and/or fillers in the liquid coating composition preferably is between 0 % and 50 %, more preferably between 2 % and 40 %.
  • the liquid coating composition resin can be applied to the substrate by any coating process suitable thereto. Examples thereof are brushing, dipping, flow coating, roller coating or blade coating, but especially by spraying.
  • the liquid coating materials are generally cured within a temperature range from 20 °C to 160 °C, preferably from 23 °C to 140 °C in for example from five minutes to ten days, more in particular from 15 minutes to 120 minutes.
  • the process of the invention described supra further comprises a step of converting a hydroxyl-functional polyester or a carboxyl-functional polyester as described above into a (meth)acryloyl-functional polyester, more in particular (meth)acryloyl group end-capped polyesters.
  • the term "(meth)acryloyl' is to be understood as to encompass both acryloyl and methacryloyl compounds or derivatives as well as mixtures thereof.
  • the present invention further concerns polyesters obtained by (or obtainable by) such process of the invention.
  • An aspect of the invention concerns such (meth)acryloyl-functional polyesters obtained or prepared from a hydroxyl-functional or a carboxyl-functional polyester of the invention.
  • the hydroxyl-functional polyesters and in particular the carboxyl-functional polyesters from which the (meth)acryloyl-functional polyesters of the invention are prepared comprise, based on the total weight of the polyester, less than 20% by weight, typically less than 5% by weight, preferably less than 1% by weight, more preferably less than 0.1 % by weight of fatty acid moieties.
  • the hydroxyl-functional and in particular the carboxyl-functional polyesters from which the (meth)acryloyl-functional polyesters of the invention are prepared comprise no fatty acid moieties, in particular comprise no saturated or unsaturated dimer or trimer fatty acid moieties, more in particular comprise no saturated dimer fatty acid moieties.
  • (Meth)acryloyl-functional polyesters of the invention are particularly useful in radiation curable and/or in heat curable coating compositions, optionally in combination with one or more ethylenically unsaturated cohardeners.
  • the conversion of the carboxyl- and hydroxyl-functional polyesters of the present invention into (meth)acryloyl group end-capped polyesters may be realized through the reaction of a diisocyanate with a hydroxyalkyl(meth)acrylate and the terminal hydroxyl groups of a polyester; or from the reaction of glycidyl(meth)acrylate and the terminal carboxyl groups of a polyester.
  • a (meth)acryloyl group end-capped polyester may be obtained from the reaction of a (meth)acrylic acid and the terminal hydroxyl groups of a polyester.
  • the hydroxyalkyl(meth)acrylate used for reaction with the diisocyanate in the above reaction is preferably selected from hydroxyethyl(meth)acrylate, 2- or 3- hydroxypropyl(meth)acrylate, 2-,3-and 4-hydroxybutyl(meth)acrylate.
  • the diisocyanate used for the reaction with the hydroxyalkyl(meth)acrylate and the hydroxyl group containing polyester in the above reaction is preferably selected from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorondiisocyanate, IPDI), tetramethyl-xylenediisocyanate (TMXDI), hexamethylenediisocyanate (HDI), trimethylhexamethylenedi-isocyanate, 4,4'-diisocyanatodicyclohexyl methane, 4,4'-diisocyanatodiphenylmethane, the technical mixtures with 2,4-diisocyanatodiphenylmethane and also the higher homologues of above mentioned diisocyanates, 2,4-diisocyanatototoluene and technical mixtures of them with 2,6-diisocyanatotoluene, as
  • the conversion of the hydroxyl- or carboxyl-functional polyester into a (meth)acryloyl functional polyester can be done in a bulk process or in solvent, such as toluene, in the presence of any of the known catalysts, such as p-toluene sulfonic acid.
  • a substantially equivalent amount of hydroxyalkyl(meth)acrylate is added thereto.
  • an equivalent amount of diisocyanate is slowly added to the mixture.
  • a catalyst for the hydroxyl/isocyanate reaction can optionally be used. Examples of such catalysts include these listed above for accelerating the crosslinking reaction. These catalysts are preferably used in an amount of 0 to 1 % with respect to the weight of the polyester.
  • a substantially equivalent amount of (meth)acrylic acid is added to the hydroxyl-functional polyester of the invention.
  • the reaction preferably is done in 10 % to 50 % by weight of solvent such as toluene, cyclohexane and/or heptane, at a temperature of from about 80 °C to about 120 °C in the presence of from 0.1 % to 5 % by weight of a catalyst such as suphonic acid or sulfuric acid, which can be rinsed out after completion of the reaction.
  • a catalyst for the acid/epoxy reaction can optionally be used. Examples of such catalysts include these mentioned above for accelerating the crosslinking reaction. These catalysts are preferably used in an amount of 0.05 to 1 % with respect to the weight of the polyester.
  • the degree of progression of the reaction typically is monitored by determination of the properties of the polyester obtained, for example the hydroxyl number, the acid number, the degree of unsaturation and/ or the content of free glycidyl(meth)acrylate or hydoxyalkyl(meth)acrylate.
  • (Meth)acryloyl-functional polyesters of the invention are preferably characterized by a degree of unsaturation of from 0.15 to 5.00, usually from 0.15 to 4.00, milliequivalents of double bonds per gram of polyester.
  • the degree of unsaturation ranges from 0.35 to 3.00, more in particular from 0.35 to 2.50 milliequivalents of double bonds per gram of polyester.
  • the degree of telechelic unsaturation of the (meth)acryloyl functional polyesters of the invention ranges of from 0 to 5.0, typically from 0 to 2.5, more preferably from 0 to 2 milliequivalents of double bonds per gram of polyester.
  • Prefered (meth)acryloyl functional polyesters for use in powder coatings have a number average molecular weight (Mn), measured by gel permeation chromatography (GPC), of at least 400 daltons, typically at least 550 daltons, preferably of at least 850 daltons, more preferably of at least 1200 daltons.
  • Mn number average molecular weight measured by gel permeation chromatography
  • Prefered (meth)acryloyl functional polyesters for use in radiation curable coating compositions have a number average molecular weight (Mn), measured by gel permeation chromatography (GPC), of at least 350 daltons, typically at least 400 daltons, preferably of at least 550 daltons, more preferably of at least 750 daltons.
  • Mn number average molecular weight measured by gel permeation chromatography
  • Yet another aspect of the invention concerns a coating composition
  • a coating composition comprising at least one (meth)acryloyl-functional polyester of the invention, and, preferably, further comprising at least one ethylenically unsaturated oligomer and/or monomer.
  • the ethylenically unsaturated oligomer preferably is a polyfunctional (meth)acrylate oligomer.
  • polyfunctional is meant to designate an oligomer having at least two unsaturated groups selected from acrylate and/or methacrylate groups.
  • the coating composition may be a radiation curable coating composition or, alternatively, a thermosetting coating composition.
  • thermosetting and/or radiation curable composition comprising at least one at least one hydroxyl-functional polyester, carboxyl-functional polyester and/or a (meth)acryloyl-functional polyester as described above.
  • a thermosetting coating composition more in particular a thermosetting powder coating composition, is just one particular example.
  • the hydroxyl-functional or carboxyl-functional polyesters, and in particular the carboxyl-functional polyesters, present in a thermosetting powder coating composition according to the invention comprise, based on the total weight of the polyester, less than 20% by weight, typically less than 5% by weight, preferably less than 1 % by weight, more preferably less than 0.1 % by weight of fatty acid moieties.
  • the hydroxyl-functional or carboxyl-functional polyesters, and in particular the carboxyl-functional polyesters, that are used in a powder coating composition according to the invention comprise no fatty acid moieties, in particular comprise no saturated or unsaturated dimer or trimer fatty acid moieties, more in particular comprise no saturated dimer fatty acid moieties.
  • thermosetting powder coating compositions of the present invention advantageously comprise substantially no semi-crystalline polyesters.
  • thermosetting powder coating compositions of the present invention comprise less than 10% by weight, in general less than 5% by weight of semi-crystalline polyesters.
  • thermosetting powder coating compositions of the present invention comprise no semi-crystalline polyesters.
  • polyester resin comprising at least one polyester of the invention.
  • the polyester may be any of the polyesters described above, id est a hydroxyl-functional polyester, a carboxyl-functional polyester and/or a (meth)acryloyl-functional polyester as described above.
  • the hydroxyl-functional, carboxyl-functional and/or (meth)acryloyl-functional polyester resins of the present invention optionally comprise from 0 to 10 % by weight of an acrylic copolymer such as claimed in WO 2009/095460 .
  • this acrylic copolymer is added in amount of at least 0.5 % by weight, more preferably at least 1 % by weight based on the polyesters.
  • this acrylic copolymer is added in amount of at most 5 % by weight, more preferably at most 3 % by weight based on the polyesters.
  • the acrylic copolymer typically is added to the polyesters of the invention, while in the molten stage, during its synthesis or at the end of its synthesis, preceding or during discharging.
  • Thermosetting coating compositions and in particular thermosetting powder coating compositions are just one aspect of the invention.
  • the polyester of the present invention is advantageously formulated with at least one crosslinker thus constituting the binder of the coating formulation.
  • one or more cohardeners can be present in the (thermosetting) coating composition such as ethylenically unsaturated monomers and/or oligomers as further described.
  • thermosetting coating composition comprising at least one polyester of the present invention and further comprising at least one cross-linker capable of reacting with the polyesters' functional groups. More in particular, the thermosetting coating composition comprises at least one hydroxyl-functional polyester of the invention and/or at least one carboxyl-functional polyester of the invention and/or at least one (meth)acryloyl-functional polyester of the invention.
  • crosslinkers that can be combined with the polyesters of the present invention are preferably selected from polyepoxy compounds, ⁇ -hydroxyalkylamide containing compounds, or polyisocyanate compounds and their mixtures.
  • Preferred polyepoxy compounds are solid at room temperature and contain at least two epoxy groups per molecule.
  • Triglycidyl isocyanurates such as the one marketed under the name Araldite®PT810
  • blends of diglycidyl terephthalate and triglycidyl trimellitates such as those commercialized under the name of Araldite®PT910 and Araldite®PT912
  • bisphenol A based epoxy resins such as those commercialized under the names Araldite® GT 7004 or DER® 692, are especially preferred.
  • Acrylic copolymers containing glycidyl groups obtained from glycidyl (meth)acrylate, at least one alkyl(meth)acrylic monomer and optionally one or more ethylenically monounsaturated monomers different from the alkyl(meth)acrylic monomers or glycidyl (meth)acrylate monomers such as described in WO 91/01748 may also be used.
  • ⁇ -hydroxyalkylamides which contain at least one, preferably two, bis( ⁇ -hydroxyalkyl)amide groups are especially preferred. Such compounds have for example been described in US-A-4727111 .
  • polyisocyanate crosslinking compounds include those which are based on isophorone diisocyanate blocked with ⁇ -caprolactam, commercially available as Vestagon®B1530, Ruco®NI-2 and Cargill®2400 or toluene-2,4-diisocyanate blocked with ⁇ -caprolactam, commercially available as Cargill®2450, and phenol-blocked hexamethylene diisocyanate.
  • Another class of blocked polyisocyanate compounds which may be employed are adducts of the 1,3-diazetidine-2,4-dione dimer of isophorone diisocyanate and a diol, wherein the ratio of NCO to OH-groups in the formation of the adduct is about 1:0.5 to 1:0.9, the mole ratio of diazetidinedione to diol is from 2:1 to 6:5, the content of free isocyanate groups in the adduct is not greater than 8 weight percent and the adduct has a molecular weight of about 500 to 4000 and a melting point of about 70 to 130°C.
  • Such an adduct is commercially available under the name Vestagon® BF1540.
  • thermosetting coating compositions based on unsaturated polyesters, in particular based on the (meth)acryloyl functional polyesters of the invention are considered, polymerization initiators such as azobis-based initiators or peroxides can be added to the formulation.
  • these initiators include 2,2' azobisisobutylnitrile, 2,2' azobis(2,4-dimethylvaleronitrile), laurylperoxide, di-t-butylperoxide, bis(4-t-butylcyclohe-xyl)peroxydicarbonate, t-butylperoxy(2-ethylhexanoate), methylethylketone peroxide and benzoylperoxide.
  • cohardeners selected from ethylenically unsaturated monomers and/or oligomers can be added, of which particularly suited examples are given infra.
  • Yet another aspect of the invention concerns a radiation curable coating composition
  • a radiation curable coating composition comprising at least one (meth)acryloyl-functional polyester of the invention and at least one ethylenically unsaturated monomer and/or oligomer.
  • the (meth)acryloyl-functional polyester of the invention advantageously is formulated with one or more ethylenically unsaturated monomers and/or oligomers, thus constituting the binder of the coating formulation.
  • the binder may further comprise at least one photo-initiator, and, optionally, at least one photo-activator. Photo-initiators are typically added when the radiation curable composition of the invention is cured under UV radiation or actinic radiation but is not needed when cured using e.g. electron beams.
  • the photo-initiators which can be used according to the present invention are chosen from those commonly used for this purpose.
  • Photo-initiators which can be used, are e.g. aromatic carbonyl compounds, such as benzophenone and its alkylated or halogenated derivatives, anthraquinone and its derivatives, thioxanthone and its derivatives, benzoin ethers, aromatic or non-aromatic alphadiones, benzil dialkyl acetals, acetophenone derivatives and phosphine oxides.
  • aromatic carbonyl compounds such as benzophenone and its alkylated or halogenated derivatives, anthraquinone and its derivatives, thioxanthone and its derivatives, benzoin ethers, aromatic or non-aromatic alphadiones, benzil dialkyl acetals, acetophenone derivatives and phosphine oxides.
  • photo-initiators are, for example, 2,2'-diethoxy1acetophenone, 2- ,3- or 4-bromoacetophenone, 2,3-pentanedione, hydroxycyclohexylphenylketone, benza1dehyde, benzoin, benzophenone, 9,10-dibromoanthracene, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 4,4'-dichlorobenzophenone, xanthone, thioxanthone, benzildimethylketal, diphenyl (2,4,6-trimethylbenzyl)phosphine oxide, and the like.
  • a photo-activator such as tributylamine, 2-(2-aminoethylamino)ethanol, cyclohexylamine, diphenylamine, tribenzylamine or aminoacrylates such as, for example, the addition product of a secondary amine, such as dimethylamine, diethylamine, diethanolamine, and the like, with a polyol polyacrylate, such as the diacrylate of trimethylolpropane, 1,6-hexanediol, and the like.
  • tributylamine 2-(2-aminoethylamino)ethanol
  • cyclohexylamine diphenylamine
  • tribenzylamine aminoacrylates
  • aminoacrylates such as, for example, the addition product of a secondary amine, such as dimethylamine, diethylamine, diethanolamine, and the like
  • a polyol polyacrylate such as the diacrylate of trimethylolpropane, 1,6-hexanediol
  • the radiation curable coating compositions in accordance with the invention can contain from 0 to 15 and preferably 0.5 to 8 parts of photo-initiators for 100 parts by weight of the binder.
  • a radiation curable coating composition of the invention advantageously comprises up to 20 % by weight and preferably up to 10 % of an ethylenically unsaturated monomer and/or an ethylenically unsaturated oligomer, which preferably is selected from the triacrylate and the trimethacrylate of tris(2-hydroxyethyl)isocyanurate, the epoxy acrylates and methacrylates which are formed by the reaction of an epoxy compound (for example, the diglycidyl ether of Bisphenol A with acrylic or methacrylic acid, the urethane acrylates and urethane methacrylates which are formed by the reaction of an organic di- or polyisocyanate with an hydroxyalkylacrylate or a hydroxyalkylmethacrylate and optionally a mono- and/ or polyhydroxylated alcohol (for example, the reaction product of hydroxyethyl(meth)acrylate with toluenediisocyanate or isophoronediisocyanate), the acrylic
  • a radiation curable composition of the invention advantageously comprises up to 50 % by weight, preferably up to 30 % by weight and more preferably up to 10 % by weight of an ethylenically unsaturated (hydrogenated)polyphenoxy and/or acrylic copolymer and/or semi-crystalline polyester and/or polyesteramide and/or polyurethane.
  • diluting monomers examples include: beta-carboxyethyl acrylate, butyl(meth)acrylate, methyl(meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate, isobornyl (meth)acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, octyl/decyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate, phenoxyethyl(meth)acrylate, nonylphenolethoxylate mono(meth)acrylate, 2-(-2-ethoxyethoxy)ethyl(meth)acrylate, 2-butoxyethyl (meth)acrylate, neodecanoic acid glycidyl ester
  • Yet a further aspect of the invention concerns a coating composition that can be cured by heat and by radiation.
  • a coating composition that can be cured by heat and by radiation.
  • a combination of both the principles of heat- and radiation curable coating formulations, can be introduced.
  • the coating compositions of the invention may further comprise additional substances, including rheological agents such as Rheocin R (Ashland), AC 540A (Honeywell), Disparlon PL-525 (Kusumoto), flow control agents such as Resiflow PV5 (Worlee), Modaflow (Cytec Surface Specialities), Acronal 4F (BASF), pigment dispersion agents such as Solplus D510 (Lubrizol) or Disperbyk-180 (BYK), leveling agents such as the one claimed in WO 2009/095460 and degassing agents such as benzoin (BASF) etc.
  • rheological agents such as Rheocin R (Ashland), AC 540A (Honeywell), Disparlon PL-525 (Kusumoto
  • flow control agents such as Resiflow PV5 (Worlee), Modaflow (Cytec Surface Specialities), Acronal 4F (BASF), pigment dispersion agents such as Solplus D510 (Lubrizol)
  • thermosetting or radiation curable powder coating compositions and in particular to thermosetting powder coating compositions.
  • the binder can further comprise various additional substances conventionally used in the manufacture of powder paints and varnishes. Examples thereof are tribo additives such as Additol P 950 (Cytec Surface Specialities), UV-light absorbers such as Tinuvin 900 (Ciba), hindered amine light stabilizers represented by Tinuvin 144 (Ciba), other stabilising agents such as Tinuvin 312 and 1130 (Ciba), antioxidants such as Irganox 1010 (Ciba) and stabilisers from the phosphonite or phosphite type.
  • tribo additives such as Additol P 950 (Cytec Surface Specialities)
  • UV-light absorbers such as Tinuvin 900 (Ciba)
  • Tinuvin 144 Tinuvin 144
  • other stabilising agents such as Tinuvin 312 and 1130 (Ciba)
  • antioxidants such as I
  • useful pigments and dyes are: metallic oxides such as titaniumdioxide, ironoxide, zincoxide and the like, metal hydroxides, metal powders, sulphides, sulphates, carbonates, silicates such as ammoniumsilicate, carbon black, talc, china clay, barytes, iron blues, leadblues, organic reds, organic maroons and the like.
  • the components of the powder coating composition according to the invention may be mixed by dry blending in a mixer or blender (e.g. drum mixer).
  • the premix is then in general is homogenised at temperatures of 60 °C to 100 °C in a single screw extruder such as the BUSS-Ko-Kneter or a double screw extruder such as the PRISM or APV.
  • the extrudate when cooled down, is then typically grounded to a powder with a particle size ranging from 10 to 150 ⁇ m.
  • the powder coating composition of the invention may be deposed on the substrate by use of a powder gun such as an electrostatic CORONA gun or TRIBO gun.
  • well known methods of powder deposition such as the fluidised bed technique can be used.
  • the powder advantageously in general is heated to a temperature between 100 °C and 250 °C for a time of e.g. approximately 0.5 to 30 minutes, causing the particles to flow and fuse together to form a smooth, uniform, continuous coating on the substrate surface.
  • the coating in the molten state is cured by UV irradiation or by irradiation with accelerated electron beams.
  • the cured coating is post-heated in order to get a further curing especially at these regions where curing through irradiation is incomplete (hidden zones).
  • Coating compositions of the invention can be applied to the most diverse substrates, such as, for example, paper, cardboard, wood, textile, plastics, such as polycarbonates, poly(meth)acrylates, polyolefins, polystyrenes, poly(vinyl chloride)s, polyesters, polyurethanes, polyamides, copolymers such as acrylonitrile-butadiene-styrene (ABS) or cellulose acetate butyrate, and the like as well as on metals of different nature such as e.g. copper, aluminium, steel, etc.
  • plastics such as polycarbonates, poly(meth)acrylates, polyolefins, polystyrenes, poly(vinyl chloride)s, polyesters, polyurethanes, polyamides, copolymers such as acrylonitrile-butadiene-styrene (ABS) or cellulose acetate butyrate, and the like as well as on metals of different nature such as
  • Coatings obtained from a powder coating composition according to the invention resulted in coatings exhibiting excellent flow and outstanding flexibility.
  • Coating compositions of the invention comprising at least one polyester of the present invention are as such particularly useful in coil- and food-contact applications especially can coating including these for coating the interior of metal cans more particular those holding alcoholic beverages. This is particularly the case for powder coating compositions.
  • liquid coating compositions of the invention proved very suitable these purposes and in particular for coil and can coating.
  • polyesters of the invention in particular hydroxyl-functional polyesters of the invention can also be used in the preparation of ethylenically unsaturated polymers such as a polyurethane polymer.
  • ethylenically unsaturated polymers such as a polyurethane polymer.
  • Preferred are water-dispersible polyurethane polymers.
  • water-dispersible polyurethane polymers are prepared from an isocyanate-terminated polyurethane prepolymer.
  • This isocyanate-terminated polyurethane prepolymer typically is formed by reacting at least:
  • the polyisocyanate (i) used according to the present invention for the preparation of the isocyanate-terminated polyurethane prepolymer may be an aliphatic, cycloaliphatic, or aromatic polyisocyanate as well known in the art. Diisocyanates or adducts thereof are often preferred.
  • the total amount of the polyisocyanate (i) used typically ranges from 10 to 60% by weight of the polyurethane polymer, preferably of from 20 to 50% by weight and more preferably of from 30 to 40% by weight.
  • the optionally present organic compounds (iii) containing at least two isocyanate-reactive groups that are used or the preparation of the isocyanate-terminated polyurethane prepolymer may be polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyesteramide polyols or polythioether polyols. Polyester polyols, polyether polyols and polycarbonate polyols are preferred. Preferred are compounds that have a number average molecular weight within the range of 400 to 5,000.
  • Isocyanate-reactive compounds (iv) typically include the compounds containing dispersing anionic groups which are necessary to render the polyurethane prepolymer self-dispersible in water such as sulfonate salt or carboxylate salt groups.
  • anionic salt functional groups selected from the group consisting of the -COOM and -SO3 M groups, preferably the -COOM group, wherein M represents an alkali metal or an ammonium, tetraalkylammonium or tetraalkylphosphonium group.
  • the pendant anionic salt group content of the polyurethane polymer may vary within wide limits but should be sufficient to provide the polyurethane with the required degree of water-dispersibility.
  • the total amount of these anionic salt group-containing compounds in the polyurethane polymer is of from 1 to 25% by weight of the polyurethane polymer, preferably of from 4 to 10% by weight.
  • the pendant hydrophilic groups that render the polyurethane prepolymer dispersible in water are acid groups that preferably are selected from carboxyl acid, sulphonic acid and/or phosphoric acid groups.
  • the preparation of the isocyanate-terminated polyurethane prepolymer can be carried out in conventional manner, by reacting a stoichiometric excess of the organic polyisocyanate(s) (i) with compounds (ii) through (iv) under substantially anhydrous conditions, at a temperature between 50 and 120 °C, preferably between 70 and 95 °C, until the reaction between the isocyanate groups and the isocyanate-reactive groups is substantially complete.
  • This reaction may be facilitated by the addition of 5 to 40% by weight, preferably 10 to 20% by weight of a solvent, in order to reduce the viscosity of the prepolymer if this would appear to be necessary.
  • Suitable solvents used either alone or in admixture, are those which are unreactive with isocyanate groups such as ketones, esters and amides such as N,N-dimethylformamide, N-cyclohexylpyrrolidine and N-methylpyrrolidone.
  • ketones and esters with a relatively low boiling point such as acetone, methyl ethyl ketone, diisopropyl ketone, methyl isobutyl ketone, methyl acetate and ethyl acetate.
  • the preparation of the isocyanate-terminated polyurethane prepolymer may be carried out in the presence of any of the known catalysts suitable for polyurethane preparation such as amines and organometallic compounds.
  • the reactants (i) through (iv) are generally used in proportions corresponding to a ratio of isocyanate groups to isocyanate-reactive groups of from about 1.1:1 to about 4:1, preferably from about 1.3:1 to 3:1.
  • Any acid groups which may be present in the polyurethane prepolymer are preferably converted to anionic salt groups by neutralization of said groups, before or simultaneously with the preparation of an aqueous dispersion of this prepolymer.
  • the dispersion process of the polyurethane prepolymer is well known to those skilled in the art, and needs rapid mixing with a high shear rate type mixing head.
  • the polyurethane prepolymer is added to the water under vigorous agitation or, alternatively, water may be stirred into the prepolymer.
  • Suitable neutralizing agents include volatile organic bases and/or non-volatile bases as well known in the art.
  • the total amount of these neutralizing agents should be calculated according to the total amount of acid groups to be neutralized. Preferably they are used in an excess of from 5 to 30% by weight, preferably 10 to 20% by weight.
  • the isocyanate functional prepolymer thus obtained further can be put into reaction with an active hydrogen-containing chain extender (v) and/or an unsaturated compound (vi) that have in their molecule at least one unsaturated function, such as acrylic, methacrylic or allylic functions and at least one nucleophilic function capable of reacting with isocyanates.
  • an active hydrogen-containing chain extender (v) and/or an unsaturated compound (vi) that have in their molecule at least one unsaturated function, such as acrylic, methacrylic or allylic functions and at least one nucleophilic function capable of reacting with isocyanates.
  • the acrylic functionality is preferred for its higher reactivity.
  • Particularly suitable are the acrylic or methacrylic esters with polyols, in wich at least one hydroxy functionality remains free, like hydroxyalkyl(meth)acrylates having 1 to 20 carbon atoms in the alkyl group and having a linear or branched structure.
  • Examples of mono-unsaturated compounds are hydroxyethylacrylate, hydroxypropylacrylate or hydroxybutylacrylate and the like.
  • Examples of polyunsaturated compounds are trimethylolpropane diacrylates, glycerol diacrylates, pentaerythritol triacrylate, ditrimethylolpropane triacrylate and their polyethoxylated, polypropoxylated or bloc copolymer equivalents.
  • Those products that provide a final composition with a non-irritant character are preferred. For this reason, the monounsaturated products as well as the ditrimethylolpropanetriacrylate are especially appropriate.
  • the acrylated chain terminating agent (vi) can be used in such a manner that it is fully converted during the reaction with the available isocyanate groups of the polyurethane prepolymer, i.e. the molar ratio of the said isocyanate groups to the hydroxyl groups is preferably between 1.0 and 2.0. It might be wished for very specific requirements that this ratio is inferior to 1. In particular, it is possible to add non-hydroxylated polyunsaturated compounds that will not react with the isocyanate groups of the prepolymer, and in an excess between 5-50%, preferably between 20-30% based on the weight of the prepolymer to enhance the crosslinking density of the polymer after irradiation.
  • Aqueous polyurethane polymer dispersions may be prepared by dispersing the isocyanate- and/or ethylenically unsaturated group terminated polyurethane prepolymer (optionally in the form of a solution in an organic solvent) in an aqueous medium, and optionally chain-extending the prepolymer with an active hydrogen-containing chain extender (v) in the aqueous phase.
  • the active hydrogen-containing chain extender (v) which may be used to react with the isocyanate-terminated polyurethane prepolymer is suitably a water-soluble aliphatic, alicyclic, aromatic or heterocyclic primary or secondary polyamine having up to 80, preferably up to 12 carbon atoms, or water. In the latter case, a fully reacted polyurethane polymer is obtained with no residual free isocyanate groups.
  • Chain extension reaction is generally carried out at a temperature between 5°C and 90°C, preferably between 20°C to 50°C.
  • the chain extender is other than water, for example a polyamine
  • it may be added to the prepolymer before or after the dispersion in an aqueous medium containing the neutralizing agent for the chain-pendant acid groups.
  • the prepolymer may be chain extended to form the polyurethane polymer while dissolved in an organic solvent, followed by the addition of water to the polymer solution until water becomes the continuous phase and the subsequent removal of the solvent by distillation to form a pure aqueous dispersion of the polyurethane polymer.
  • Localized amine concentration gradients are preferably avoided by forming previously an aqueous solution of the polyamine used for the chain extension and adding slowly this solution to the polyurethane prepolymer dispersion.
  • An aspect of the invention relates to an ethylenically unsaturated polymer, in particular a water-dispersible polyurethane as described above.
  • Yet another aspect of the invention relates to a radiation curable composition, more in particular an aqueous radiation curable composition comprising at least one ethylenically unsaturated polymer, in particular at least one water-dispersible polyurethane according to the invention.
  • Coating compositions comprising such polymers exhibit good flexibility and stain and solvent resistance.
  • photoinitiators When liquid radiation curable coating compositions are considered, whether solvent-less, solvent based or water-dispersed, one or more photoinitiators well known in the art may be added. Photoinitiators preferably are used in a concentration from 0.1 to 10%.
  • the radiation curable compositions of the invention also may contain inhibitors such as ydroquinone, toluhydroquinone, monomethyl ether hydroquinone, tert-butyl hydroquinone, di-tert-butyl hydroquinone and/or phenothiazine.
  • the amount of inhibitor used is preferably from 0 to 0.5% by weight.
  • the radiation curable composition can be applied by any conventional method including dip coating, spray coating, electrostatic coating, film coating, curtain coating, vacuum application, roll coating, knife coating or by engraving cylinders and the like to any substrate including wood, fabrics, paper, plastics, fiberboard, cardboard, glass, glass fibers, ceramics, concrete, leather, metals and the like, for industrial or domestic purposes.
  • the application of the curable resin to the substrate can be done at any suitable temperature, usually from 10 to 80 °C, preferably at room temperature.
  • the latter is cured.
  • Solvent or water, where present, can be evaporated before or during the curing process.
  • Curing, i.e. polymerization can be achieved by any suitable means well known to those skilled in the art.
  • the irradiation curing can be done by using UV light or ionizing radiation such as gamma rays, X-rays or electron beam. In the process according to the invention, electron beam and especially UV-radiation are preferred.
  • a photoinitiator it is not necessary to use a photoinitiator, since this type of radiation produces by itself a sufficient quantity of energy to produce free radicals and to ensure that curing is extremely rapid.
  • a process for coating an article, partially or entirely, with a with a coating composition comprising the steps of applying to at least one surface of the article a coating composition, followed by a step of curing the applied coating composition.
  • the coating used can be a powder coating composition, that is either a thermosetting or a radiation curable coating composition, more in particular is a thermosetting powder coating composition.
  • the coating composition that is used can, however, also be a liquid thermosetting or radiation curable coating composition.
  • a mixture of 215.0 parts of isosorbide, 19.8 parts of glycerol along with 1.0 part of tetra-n-butyl titanate catalyst is placed in a conventional four-neck round bottom flask.
  • the flask contents are heated while stirring, under nitrogen to a temperature of circa 160°C. Thereupon 572.0 parts of recycled polyethylene terephthalate are slowly added while stirring and while the mixture is gradually heated to a temperature of 230°C.
  • a mixture of 245.4 parts of succinic acid along with 1.0 part of tributylphosphite and 1.0 part of butylstannoic acid are added to the hydroxyl functionalized prepolymer of step 1. Thereupon the mixture is gradually heated to 230°C. After a two-hour period at 230°C a vacuum of 50 mm Hg is gradually applied until following characteristics are obtained:
  • Example 2 In the same way as in Example 1, a mixture of 128.4 parts of isosorbide, 21.5 parts of glycerol 1.0 part of tetra-n-butyl titanate and 738.7 parts of recycled polyethylene terephthalate are reacted for 3 hours at a temperature of 230°C. Vacuum then gradually is applied in order to distill of 70.0 parts of ethylene glycol so that a hydroxyl-functional prepolymer with a hydroxyl number of 100 mg KOH/g is obtained. The reaction mixture then is cooled down to 160°C.
  • Example 2 In the same way as in Example 1, a mixture of 204.8 parts of isosorbide, 10.7 parts of glycerol 1.0 part of tetra-n-butyl titanate and 620.2 parts of recycled polyethylene terephthalate are reacted for 3 hours at a temperature of 230°C until a hydroxyl number of 200 mg KOH/g is obtained. The reaction mixture then is cooled down to 160°C.
  • Example 2 In the same way as in Example 1, a mixture of 210.2 parts of isosorbide, 15.2 parts of glycerol 1.0 part of tetra-n-butyl titanate and 650.8 parts of recycled polyethylene terephthalate are reacted for 3 hours at a temperature of 230°C until a hydroxyl number of 220 mg KOH/g is obtained. The reaction mixture then is cooled down to 160°C.
  • step 2 To the hydroxyl functional prepolymer of step 1, standing at 160°C, 168.0 parts of succinic acid along with 1.0 part of tributylphosphite and 1.0 part of butylstannoic acid then are added. Thereupon the mixture is gradually heated to 230°C. After a two-hour period at 230°C a vacuum of 50 mm Hg is gradually applied until following characteristics are obtained:
  • Example 2 In the same way as in Example 1, a mixture of 229.1 parts of isosorbide, 10.2 parts of glycerol 1.0 part of tetra-n-butyl titanate and 595.3 parts of recycled polyethylene terephthalate are reacted for 3 hours at a temperature of 230°C. The reaction mixture then is cooled down to 160°C.
  • the carboxyl-functional polyester is cooled down to 150°C and 0.9 parts of di-t-butylhydroquinone along with 4.9 parts of ethyltriphenylphosphonium bromide are added. Subsequently 71.7 parts of glycidylmethacrylate is slowly added (30 minutes) while stirring under oxygen. An hour after the addition is ended, a (meth)acryloyl unsaturated polyester with the following characteristics is obtained
  • polyesters of Examples 1 to 3 are formulated with Araldite GT 7004, thus constituting the binder,
  • the polyester of Example 4 is formulated with Vestagon B1530, thus constituting the binder, accordingly the white powder formulation (1) as given below: Binder 690.6 parts Kronos 2310 296.0 parts Modaflow P6000 9.9 parts Benzoin 3.5 parts
  • the polyester of Example 1 is formulated with Primid XL552, thus constituting the binder, accordingly the brown powder formulation (2) as given below: Binder 783.3 parts Bayferrox 130 44.4 parts Bayferrox 3950 138.0 parts Carbon Black FW2 10.9 parts Modaflow P6000 9.9 parts Benzoin 3.5 parts
  • polyester of Example 5 is formulated accordingly the powder formulation (3) as given below: Polyester Example 5 750.0 parts Kronos 2310 250.0 parts Irgacure 2959 12.5 parts Irgacure 819 12.5 parts Modaflow P6000 10.0 parts
  • the powders are prepared first by dry blending of the different components and then by homogenisation in the melt using a PRISM 16 mm L/D 15/1 twin screw extruder at an extrusion temperature of 85°C.
  • the extrudate is ground in a grinder of Alpine 100UPZ (from the company Alpine and subsequently sieved in order to obtain a size of the particles between 10 and 110 ⁇ m.
  • the powder thus prepared is deposited on cold rolled steel with a thickness of 0.8 mm, by electrostatic deposition using the GEMA - Volstatic PCG 1 spraygun at a voltage of 60 kV, in such a way that a film thickness of the cured coating of about 80 ⁇ m is obtained.
  • the panels comprising the coatings obtained from the polyesters of Example 1 to 4 then are transferred to an air-ventilated oven, where curing proceeds for 15 minutes at a temperature of 180°C for the coatings of Example 6 to 10.
  • the panel comprising the coating obtained from the polyesters of Example 5 then is subjected to melting step in a medium wavelength infrared/convection oven (Triab) at a temperature of 140°C during a time of approximately 3 minutes, and subsequently is subjected to irradiation with ultraviolet light emitted by a 160 W/cm Gallium-doped and/or a 160 W/cm medium-pressure mercury vapour UV-bulb (Fusion UV Systems Ltd.) with a total UV-dose of 4000 mJ/cm 2 .
  • Triab medium wavelength infrared/convection oven
  • the powder coatings comprising the polyesters of the present invention show an outstanding flexibility (DI/RI), confirmed by the T-bending test.
  • Example 10 also has been submitted to.the Q-UV accelerated weathering tester (Q-Panel Co) according to ASTM G53-88 (standard practice for operating light and water exposure apparatus - fluorescent UV/condensation type - for exposure of non metallic materials).
  • Q-UV accelerated weathering tester Q-Panel Co
  • the panels used in the Q-UV are yellow chromated aluminium ones.
  • the gloss 60° value is reduced to 50% of its initial value.
  • a polyester-polyol is synthesized as follows: A mixture of diethylene glycol (DEG), isosorbide (isoS) and an esterification-catalyst (300-500 ppm Sn corresponding to 0.15-0.25 % by weight of Fascat 4102) are heated to 160°C in a conventional four neck round bottom flask equipped with a stirrer, a distillation column connected to a water cooled condenser, an inlet for nitrogen and a thermocouple attached to a thermoregulator.
  • DEG diethylene glycol
  • isoS isosorbide
  • esterification-catalyst 300-500 ppm Sn corresponding to 0.15-0.25 % by weight of Fascat 4102
  • the reaction mixture When all PET is added, the reaction mixture is kept for 2 hrs at 230°C. The reaction mixture then is cooled down to about 150°C, and succinic acid (SA) and isophthalic (iPA) are added. When all succinic acid and isophthalic acid is added, the reaction mixture is heated again to 230°C.
  • SA succinic acid
  • iPA isophthalic
  • polyester-polyols of examples 12 and 13 were prepared: Table 2 Example 12 Example 13 PET 290.162 206.03 iPA 151.843 89.96 SA 198.178 324.49 DEG 190.612 341.36 IsoS 262.496 156.70 -H 2 O -93.446 -118.54 OHN (mg KOH/g) 89 125.7 AN (mg KOH/g) 8.8 5.7
  • the mixture then is washed three times with 10% by weight of the reaction mixture of a 16% by weight Na 2 SO 4 /water solution, and dried via azeotropic distillation. Subsequently the toluene is distilled of under a vacuum of about 30 mm Hg and the reaction product is filtered.
  • tri(propyleneglycol) diacrylate is added in such an amount that the final mixture consists of 80% by weight of the acrylate end-capped polyester and of 20% by weight of tri(propyleneglycol) diacrylate.
  • 211.8 parts of the polyester of Example 12 are diluted, at room temperature, in 141.2 parts of methoxypropylacetate by using a Dispermat with a 25 mm diameter dispersing disc at 1200 rpm. Then, 297.1 parts of Kronos 2190 (TiO 2 -pigment) is gradually added in a 5 minutes period to the polyester solution while mixing at 1250 to 1800 rpm. When the pigment addition is completed, the mixing speed is increased to 5750 rpm for 10 minutes until a pigment agglomerate size of less than 4 ⁇ m, as measured by a Grindometer, is obtained.
  • Kronos 2190 TiO 2 -pigment
  • the paint formulation thus obtained, after sieving over a 20 ⁇ m sieve, then is applied, using a block applicator with a gauge of 60 ⁇ m, on 0.21 mm thickness primed aluminum panels. After a 45 sec. pre-drying period at room temperature, the panels are transferred to a preheated bench where curing proceeds for 30 sec. at 240°C (metal temperature). The panels, after standing for 30 sec. at 240°C then are quenched under rinsing tap water and dried for evaluation.
  • the coating obtained from the formulation of Example 15 proves to be pasteurization stable (30' at 80°C), when applied on aluminum panels and retortable for 30 min. at 105 °C and 30 min. at 121°C, when applied on tin panels which both are typical requirements for outside can coating for drinks and food respectively.
  • Example 16 The radiation curable formulation of Example 16 then is applied on LENETA paper (Form WA - plain white charts) using a bar coater of 20 ⁇ m and cured at a speed of 30 m/min using a UV source consisting of a medium pressure mercury vapor lamp with a power of 80 W/cm, whose radiation is concentrated with the aid of a semi-elliptical reflector and with a total dose of 265 mJ/cm 2 .
  • a UV source consisting of a medium pressure mercury vapor lamp with a power of 80 W/cm, whose radiation is concentrated with the aid of a semi-elliptical reflector and with a total dose of 265 mJ/cm 2 .
  • the clear coating thus obtained, proves an outstanding resistance against a 10% ammonia in water solution, against a 50% ethanol in water solution and against isopropanol.
  • a free film of about 100 ⁇ m thickness obtained after curing at a speed of 20 m/min using 5 successive UV sources, each consisting of a medium pressure mercury vapor lamp with a power of 80 W/cm, whose radiation is concentrated with the aid of a semi-elliptical reflector, and with a total dose of 2400 mJ/cm 2 , is characterized by a Young Modulus of 23.5 Mpa and proves an Elongation, at break, of 43.5 %, indicating a high flexibility of the coating.
  • reaction mixture When all PET is added, the reaction mixture is kept for 2 hrs at 230°C. The reaction mixture then is cooled down to about 150°C, and 218.05 parts of succinic acid and 83.61 parts of isophthalic are added. When all succinic acid and isophthalic acid is added, the reaction mixture is heated again to 230°C
  • vacuum is gradually applied till 50 mm Hg and maintained until an acid number of 3 mg KOH/g and a hydroxyl number of 165 mg KOH/g is obtained.
  • This polyester-polyol is then used in the preparation of a radiation curable polyurethane dispersion.
  • a double-wall glass reactor equipped with a mechanical stirrer, a thermocouple, a vapor condenser and a dropping funnel is charged with.
  • 190.0 parts of the polyester of Example 17 53.2 parts of dimethylol propionic acid, 24.5 parts of cyclohexane dimethanol, 332.2 parts of tetramethylxylylenediisocyanate, 2.3 parts of Irganox 245, 4.6 parts of Tinuvin 328, 4.6 parts of Tinuvin 622 and 0.6 parts of dibutyltinlaurate solution in acetone (at 10%) as reaction catalyst.
  • the reaction mixture is heated up to 90°C with stirring, and the condensation process is maintained until the isocyanate content reaches 1.67 meq/g.
  • the polyurethane prepolymer is cooled down to 70° C and 0.18 parts of 4-methoxyphenol dissolved in 314.9 parts of pentaerytrytoltriacrylate (PETIA) is added to the vessel.
  • PETIA pentaerytrytoltriacrylate
  • the reaction mixture is kept at 70°C, and the end-capping process is maintained until the isocyanate content reaches 0.42 meq/g.
  • 40.6 parts of triethylamine is added as neutralizing agent in the warm prepolymer until homogenous. 1722 parts of water at room temperature is loaded in the reactor under vigorous mixing and beyond the phase inversion point.
  • a stable polymer dispersion is obtained after about 5 minutes of vigorous mixing, but the agitation is maintained over a period of 1 hour.
  • the product is filtered over a 100 ⁇ m sieve. It has a dry content of 32.9%, a pH of 7.8, a particle size of 54 nm and a grits content of ⁇ 100 mg/l. It contains no solvent.
  • the dispersions are formulated with 1.5% of Irgacure 500 (a photoinitiator marketed by Ciba). They are applied on white PVC, and cured under UV-light, 80W/cm whose radiation is concentrated with the aid of a semi-elliptical reflector, at 5 m/min and with a total dose of 1100 mJ/cm2.
  • Irgacure 500 a photoinitiator marketed by Ciba
  • the coating thus obtained proves good flexibility and stain resistance as well as an outstanding resistance against a 50% ethanol-solution and against isopropanol.

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Claims (16)

  1. Polyester hydroxyfonctionnel ou carboxyfonctionnel comprenant des fractions
    (a) d'acide téréphtalique et/ou d'acide isophtalique,
    (b) d'éthylène glycol,
    (c) d'un dianhydrohexitol, et
    (d) d'un ou plusieurs acides dicarboxyliques à chaîne linéaire,
    le polyester ayant un poids moléculaire moyen en nombre, tel que mesuré par chromatographie par perméation de gel, de 400 à 15 000 daltons, de préférence de 550 à 15 000 daltons.
  2. Polyester selon la revendication 1 comprenant, rapporté au poids total du polyester :
    (a) de 10 % à 80 % en poids de fractions d'acide téréphtalique et/ou d'acide isophtalique,
    (b) de 5 % à 35 % en poids de fractions d'éthylène glycol,
    (c) de 5 % à 40 % en poids de fractions de dianhydrohexitol,
    (d) de 5 % à 40 % en poids de fractions d'acides dicarboxyliques à chaîne linéaire, et
    (e) de 0 % à 40 % en poids de fractions d'un ou plusieurs autres polyols (e1) et/ou d'un ou plusieurs autres polyacides (e2).
  3. Polyester selon l'une quelconque des revendications précédentes, dans lequel le dianhydrohexitol est l'isosorbide.
  4. Polyester à fonctionnalité (méth)acryloyle préparé à partir d'un polyester de l'une quelconque des revendications 1 à 3.
  5. Composition de revêtement comprenant au moins un polyester de l'une quelconque des revendications 1 à 4.
  6. Article recouvert, partiellement ou entièrement, d'une composition de revêtement de la revendication 5.
  7. Procédé de production d'un polyester comprenant une étape de
    (1) glycolyse d'un téréphtalate de polyéthylène et/ou d'un isophtalate de polyéthylène avec un dianhydrohexitol, suivi
    (2) si nécessaire, d'une ou plusieurs étapes supplémentaires,
    dans lequel est produit un polyester qui est hydroxyfonctionnel ou carboxyfonctionnel, et qui a un poids moléculaire moyen en nombre, tel que mesuré par chromatographie par perméation de gel, de 400 à 15 000 daltons, de préférence de 550 à 15 000 daltons.
  8. Procédé selon la revendication 7 dans lequel l'étape (2) comprend une étape d'extension de chaîne et/ou de carboxylation d'un polyester hydroxyfonctionnel obtenu précédemment.
  9. Procédé selon la revendication 8 dans lequel pour ladite extension de chaîne et/ou ladite carboxylation un ou plusieurs acides dicarboxyliques à chaîne linéaire sont utilisés.
  10. Procédé selon les revendications 7 à 9 dans lequel le téréphtalate de polyéthylène et/ou l'isophtalate de polyéthylène utilisés à l'étape (1) sont fournis sous la forme d'un matériau comprenant ledit téréphtalate de polyéthylène et/ou ledit isophtalate de polyéthylène.
  11. Procédé selon la revendication 10 dans lequel ledit matériau est un matériau recyclé.
  12. Procédé selon la revendication 11 dans lequel ledit matériau recyclé est du téréphtalate de polyéthylène recyclé.
  13. Procédé selon l'une quelconque des revendications 7 à 12 dans lequel ledit dianhydrohexitol est un isosorbide obtenu à partir d'une matière première biosourcée.
  14. Procédé selon l'une quelconque des revendications 7 à 13 comprenant en outre une étape de transformation d'un polyester hydroxyfonctionnel ou d'un polyester carboxyfonctionnel ainsi obtenu en un polyester à fonctionnalité (méth)acryloyle.
  15. Procédé selon la revendication 14 dans lequel un polyester coiffé aux extrémités par un groupe (méth)acryloyle est obtenu à partir de la réaction d'un diisocyanate avec un (méth)acrylate d'hydroxyalkyle et avec les groupes hydroxyle terminaux d'un polyester hydroxyfonctionnel, ou à partir de la réaction d'un acide (méth)acrylique avec les groupes hydroxyle terminaux d'un polyester hydroxyfonctionnel.
  16. Procédé selon la revendication 14 dans lequel un polyester coiffé aux extrémités par un groupe (méth)acryloyle est obtenu à partir de la réaction de (méth)acrylate de glycidyle et des groupes carboxyle terminaux d'un polyester carboxyfonctionnel.
EP20100775838 2009-11-13 2010-11-12 Polyesters pour revêtements Active EP2499183B1 (fr)

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EP20090175912 EP2325229A1 (fr) 2009-11-13 2009-11-13 Polyesters pour revêtements
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TW201129603A (en) 2011-09-01
US8637581B2 (en) 2014-01-28
TWI496811B (zh) 2015-08-21
EP2325229A1 (fr) 2011-05-25
CN102597053A (zh) 2012-07-18
PL2499183T3 (pl) 2014-11-28
KR20120100987A (ko) 2012-09-12
CN102597053B (zh) 2014-04-09
EP2499183A1 (fr) 2012-09-19
KR101729803B1 (ko) 2017-04-24
JP5735525B2 (ja) 2015-06-17
JP2013510917A (ja) 2013-03-28
WO2011058130A1 (fr) 2011-05-19
ES2487629T3 (es) 2014-08-22

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